CN105860406A - Olefin polymer, preparation method and application thereof - Google Patents
Olefin polymer, preparation method and application thereof Download PDFInfo
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- CN105860406A CN105860406A CN201510026204.7A CN201510026204A CN105860406A CN 105860406 A CN105860406 A CN 105860406A CN 201510026204 A CN201510026204 A CN 201510026204A CN 105860406 A CN105860406 A CN 105860406A
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Abstract
The invention discloses an olefin polymer, a preparation method and an application thereof. The olefin polymer contains a star-shaped conjugated diene homopolymer, a liner conjugated diene homopolymer and a liner conjugated diene-mono-vinyl aromatic copolymer, the molecular weight distribution of the olefin polymer is unimodal distribution, the mooney viscosity ML1+4 of the olefin polymer at the temperature of lower than 100 DEG C is 45-70, and the viscosity of a styrene solution with concentration being 5wt% of the olefin polymer is 0.02-0.04 Pa.s at the temperature of 25 DEG C. The olefin polymer can endow resin with high impact intensity and high glossiness.
Description
Technical field
The present invention relates to a kind of olefin polymer, the preparation method of a kind of olefin polymer, by the method
The olefin polymer prepared and this olefin polymer are as polystyrene resin and/or acrylic nitrile-butadiene
The application of the modifying agent of styrene resin.
Background technology
For improving the resistance to of polystyrene (PS) resin and acrylonitrile-butadiene-styrene (ABS) (ABS) resin
Impact, prior art is generally introduced therein to modification rubber.The biggest rubber size
Resin can be made to have higher impact strength, but the glossiness of resin can be reduced, less rubber size
Although ensure that the high gloss of resin, but easily imbedding in stress crack, causing resin impact resistance
Decline.Accordingly, it would be desirable to control in certain size by rubber size, reach to improve the light of resin
Pool degree, can keep again the purpose of the impact resistance of resin.In general, rubber particle size is controlled
(the benzene second of the modified rubber of 5 weight % when 25 DEG C, can be contained by the SV value controlling resin modified rubber
The viscosity of alkene solution) mode realize.
Additionally, introduce the equal poly structure of monovinylarene in modified rubber strand, not only can improve
Modified rubber intermiscibility in resin, also can improve the index of refraction of modified rubber simultaneously, makes modified rubber
The index of refraction of glue is close with the index of refraction of resin matrix, and then eliminates the light scattering within resin, tree
The glossiness of fat gets a promotion, and the transparency of resin is also improved simultaneously.
In order to improve the resistance to impact of acrylonitrile-butadiene-styrene (ABS) (ABS) resin, and keep surface
Glossiness is basically unchanged, and US4524180 discloses a kind of monovinylarene compositions, wherein disperses
There are dience rubber (polybutadiene) and butadiene and mono vinyl arenes monomer and/or ethylenic insatiable hunger
Mixture with lonitrile copolymer.US4587294 discloses a kind of continuous preparation and has high-impact performance
The preparation method of rubber, the method includes mixing aromatic hydrocarbon monomer, acrylonitrile monemer and polybutadiene
Compound and initiator introduce in the first reactor, and carry out polyreaction under high shear is stirred, so that
Rubber components inversion of phases is discrete particles, and then the first product introduces the second reactor and more
Many reactors react further.
US4639494 discloses the preparation method of a kind of resin with high-impact performance, and the method includes
Styrene carries out in the presence of butadiene rubber Raolical polymerizable, and described butadiene rubber is
By 1,3-butadiene homopolymerization or by 1,3-butadiene with styrene copolymerized obtain highly branched be polymerized
Thing, then reacts the polymer obtained with polyfunctionality halogen contained compound, wherein side chain further
Structural content is more than or equal to 60%, and 1,2 structure accounts for 18-32 weight % of polybutadiene segments, and styrene is embedding
Section content be 8-10 weight %, Mooney viscosity of rubber be 40-90, SV value be 0.06-0.09Pa s.This
Although kind of rubber has high impact strength for modified resin, but the SV value of rubber is the highest, this
Sample can cause the decline of modified resinous luster degree.
US4421895 discloses and uses the SV value line equal to or less than 0.08Pa s in the preparation of ABS
Type Styrene-Butadiene block dience rubber, it is thus achieved that have and be dispersed in substrate less than 0.7 μ m in size
In rubber grain, and therefore obtain there is high performance attractive in appearance, the ABS of high glaze.But, but
Compromise the physical mechanical feature of ABS resin, particularly resistance to impact.
In prior art, Star-shaped Low-cis-Polybutadiene rubber and line style butylbenzene block rubber many employings lithium
Series anion solution polymerization technique synthesizes, and the polymerization glue obtained must be therein molten through agglomeration process removing
Agent, after be dried through two-shipper, vulcanization bed forced air drying, briquetting, be packaged into finished product.More than considering
Described aftertreatment technology and the performance of rubber product, the Mooney viscosity (ML of polymerization glue1+4,
100 DEG C) it is to produce the leading indicator controlled, if product Mooney viscosity is too high, sizing material easy powder during cohesion
Changing, leak glue serious before causing two-shipper at glue grain sieves, the difficulty of two-shipper material feeding simultaneously, product is difficult to
By compound stalk forming；If product Mooney viscosity is the lowest, then when condensing, bad dispersibility between sizing material, easily assembles
On the one hand in bulk, easily causes condensing field, discharging pump and discharging pump to process pipelines stifled between two-shipper
Plug, on the other hand, in easily causing two-shipper, roller embraced by sizing material, not only affects drying effect, is also easily generated
Plasticizing glue, causes product gel content higher, affects resin property.
In prior art, when preparing SV value resin modified rubber between 0.02-0.40Pa s,
For design molecular weight be 50,000-60,000, coupling efficiency be the star low cis polybutadiene of 70-90%
For alkene rubber, its Mooney viscosity is typically in the range of between 30-40, and Mooney viscosity is on the low side, cohesion and rear place
Reason difficulty.And for design molecular weight be 10,000-15,000, styrene-content be that 20-40 weight % is left
For right line style butylbenzene block rubber, its Mooney viscosity is typically in the range of between 110-150, and this Mooney glues
Under degree, during cohesion, rubber efflorescence is serious, post processing difficulty.
In sum, it is badly in need of exploitation a kind of to ensure the impact strength of modified resin, can change again
It is apt to the polymer-modified of resinous luster degree.
Summary of the invention
It is an object of the invention to overcome single variety modified rubber in prior art can not meet resin simultaneously
The defect that impact strength and resinous luster require, and provide that a kind of new can to give resin high simultaneously
Impact strength and the olefin polymer of high glossiness, the preparation method of described olefin polymer, by
Olefin polymer that the method prepares and described olefin polymer as polystyrene resin and/or
The application of the modifying agent of acrylonitrile-butadiene-styrene resin.
The invention provides a kind of olefin polymer, wherein, described olefin polymer contains star-like conjugation
Diene homopolymers, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene copolymerization
Thing, the molecular weight distribution of described olefin polymer is Unimodal Distribution, and described olefin polymer is at 100 DEG C
Mooney viscosity ML1+4For 45-70, and SV value (concentration is the described olefin polymer of 5 weight %
Styrene solution viscosity at 25 DEG C) it is 0.02-0.04Pa s.
Additionally, present invention also offers the preparation method of a kind of olefin polymer, the method includes:
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer
And atent solvent is continually introduced into the continuous polymerization reaction unit including at least three series polymerizations reactor
First still in carry out the first polyreaction；
(2) conversion ratio >=97% of conjugated diene monomer described in described first still exit is controlled, and will
Polyfunctionality coupling agent is continually introduced in second polymerization reaction kettle of described continuous polymerization reaction unit
Row coupling reaction；Total coupling group in the described polyfunctionality coupling agent added in unit interval and list
The mol ratio of the described single functionality organic lithium initiator added in bit time is 0.40-0.55:1；
(3) terminator and mono vinyl arenes monomer are continually introduced into described continuous polymerization reaction unit
3rd polymerization reaction kettle contacts with the product from described second polymerization reaction kettle carry out
Dimerization is reacted, and controls mono vinyl arenes monomer described in described 3rd polymerization reaction kettle exit
Conversion ratio is >=97%；In unit interval, the addition interior with the unit interval of the described terminator of addition is described
The mol ratio of single functionality organic lithium initiator is 0.1-0.15:1.
Present invention also offers the olefin polymer prepared by said method.
Additionally, present invention also offers described olefin polymer as polystyrene resin and/or acrylonitrile-
The application of the modifying agent of butadiene styrene resin.
The present inventor finds after further investigation, in non-polar solven, uses stable
Single functionality organic lithium initiator causes conjugate diene monomer polymerization, even through polyfunctionality coupling agent part
After connection, add containing the mono vinyl arenes monomer of certain terminator, can prepare have simultaneously star-like
Conjugated diene homopolymers, linear conjugated diene homopolymers and linear conjugated alkadienes-monovinylarene
The olefin polymer of copolymer, this polymer has the suitable Mooney viscosity (Mooney viscosity at 100 DEG C
ML1+4For 45-70) and suitable SV value (0.02-0.04Pa s), and use the alkene of the present invention to gather
Resin is modified by compound, on the premise of the mechanical property ensureing resin, can be effectively improved resin
Glossiness.
Other features and advantages of the present invention will give specifically in detailed description of the invention part subsequently
Bright.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place
The detailed description of the invention described is merely to illustrate and explains the present invention, is not limited to the present invention.
The olefin polymer that the present invention provides contains star-like conjugated diolefin homopolymerization thing, linear conjugated diene
Hydrocarbon homopolymer and linear conjugated diene-monovinylarene copolymer, the molecular weight of described olefin polymer
It is distributed as Unimodal Distribution, described olefin polymer Mooney viscosity ML at 100 DEG C1+4For 45-70, and
Concentration is that the styrene solution of the described olefin polymer of 5 weight % viscosity at 25 DEG C is
0.02-0.04Pa·s。
The present invention is to conjugated diolefin homopolymerization thing star-like in described olefin polymer, linear conjugated alkadienes
The content of homopolymer and linear conjugated diene-monovinylarene copolymer is not particularly limited, example
As, on the basis of the gross weight of described olefin polymer, containing of described star-like conjugated diolefin homopolymerization thing
Amount can be 40-55 weight %, and the content of described linear conjugated diene homopolymers can be 10-15 weight
Amount %, the content of described linear conjugated diene-monovinylarene copolymer can be 35-45 weight %.
According to the present invention, in order to preferably carry when enabling described olefin polymer as modifier
The glossiness of high resin, it is preferable that on the basis of the gross weight of described olefin polymer, described line style
In conjugated diene-monovinylarene copolymer, the content of monovinylarene homopolymerization section is 20-40 weight
Amount %, more preferably 25-35 weight %.In the present invention, described monovinylarene homopolymerization section refers to
Continuously containing six and more than six on described linear conjugated diene-monovinylarene copolymer strand
Monovinylarene construction unit.Additionally, in described linear conjugated diene-monovinylarene copolymer
The content of the micro-block of monovinylarene is theoretically the lowest more good, but from the ready availability angle of raw material
Set out, it is preferable that on the basis of the gross weight of described olefin polymer, described linear conjugated diene-mono-
In vinyl-arene copolymer, the content of the micro-block of monovinylarene is 0-3 weight %, more preferably
0-2 weight %.In the present invention, the micro-block of described monovinylarene refer to described linear conjugated diene-
Continuously containing five and less than five monovinylarene structures on monovinylarene copolymer strand
Unit.
According to the present invention, in described olefin polymer, conjugated diene construction unit can be with 1, and 2-ties
Presented in structure, it is also possible to Isosorbide-5-Nitrae-structure (including cis-Isosorbide-5-Nitrae-structure and anti-form-1,4-structure)
Form exists.The present invention is to 1,2-construction unit, cis-1,4-knot in described conjugated diene construction unit
Structure unit and anti-form-1, the content of 4-construction unit is all not particularly limited, such as, with described alkene
In hydrocarbon polymer on the basis of the content of conjugated diene construction unit, in described conjugated diene construction unit
The content of 1,2-construction unit can be 5-15 weight %, and the content of cis-Isosorbide-5-Nitrae-construction unit can be
25-40 weight %, anti-form-1, the content of 4-construction unit can be 45-65 weight %；Preferably, with institute
State in olefin polymer on the basis of the content of conjugated diene construction unit, described conjugated diene structure list
In unit 1, the content of 2-construction unit can be 8-12 weight %, and the content of cis-Isosorbide-5-Nitrae-construction unit is permissible
For 30-35 weight %, anti-form-1, the content of 4-construction unit can be 55-60 weight %.
Molecular size range and the molecular weight distributing index of described olefin polymer are not had the most especially by the present invention
Limiting, such as, the number-average molecular weight of described olefin polymer can be 50,000-70,000, molecular weight
Profile exponent can be 1.5-1.8.Specifically, in described olefin polymer, described star-like conjugation two
The number-average molecular weight of olefin homo can be 48,000-65,000, preferably 50,000-63,000；Institute
The number-average molecular weight stating linear conjugated diene homopolymers can be 35,000-45,000, is preferably
38,000-42,000；The number-average molecular weight of described linear conjugated diene-monovinylarene copolymer is permissible
It is 55,000-100,000, preferably 60,000-95,000.
According to the present invention, described conjugated diene construction unit is the structure list derived from conjugated diene
Unit, the construction unit i.e. formed by conjugate diene polymerization.Described conjugated diene refers to molecular structure
In containing the various unsaturated acyclic hydrocarbons of conjugated double bond (that is ,-C=C-C=C-).Described conjugated diene
Kind can be the conventional selection of this area, is not particularly limited, such as, and described conjugated diene
C can be selected from4-C12Straight or branched conjugated diene, preferably C4-C8Straight or branched conjugated diene,
The more preferably one in butadiene, isoprene and pentadiene.
According to the present invention, described monovinylarene construction unit is the knot derived from monovinylarene
Structure unit, is i.e. polymerized the construction unit formed by monovinylarene.The kind of described monovinylarene
Class can be the conventional selection of this area, is not particularly limited, such as, and described monovinylarene
C can be selected from8-C20Monovinylarene, preferably C8-C12Monovinylarene, more preferably benzene second
One in alkene, p-methylstyrene and α-methyl styrene.
The preparation method of the olefin polymer that the present invention provides comprises the following steps:
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer
And atent solvent is continually introduced into the continuous polymerization reaction unit including at least three series polymerizations reactor
First still in carry out the first polyreaction；
(2) conversion ratio >=97% of conjugated diene monomer described in described first still exit is controlled, and will
Polyfunctionality coupling agent is continually introduced in second polymerization reaction kettle of described continuous polymerization reaction unit
Row coupling reaction；Total coupling group in the described polyfunctionality coupling agent added in unit interval and list
The mol ratio of the described single functionality organic lithium initiator added in bit time is 0.40-0.55:1；
(3) terminator and mono vinyl arenes monomer are continually introduced into described continuous polymerization reaction unit
3rd polymerization reaction kettle contacts with the product from described second polymerization reaction kettle carry out
Dimerization is reacted, and controls mono vinyl arenes monomer described in described 3rd polymerization reaction kettle exit
Conversion ratio is >=97%；In unit interval, the addition interior with the unit interval of the described terminator of addition is described
The mol ratio of single functionality organic lithium initiator is 0.1-0.15:1.
According to the present invention, the preparation of described olefin polymer can use the method for existing various routine
Implement.According to a kind of detailed description of the invention of the present invention, the preparation method of described olefin polymer is permissible
The polymerization reaction kettle of three series connection is carried out, uses the feeding manner of bottom in and top out, carry out full still behaviour
Make.Solvent, conjugated diene monomer, initiator and other reaction promoter confess one's crime still bottom add, instead
Answer material after first still stays for some time, from first still still top overflow to the second still bottom；Coupling agent is certainly
Two still bottoms add, after certain time of staying, reaction mass by two still still top overflows to the 3rd still
Bottom；Terminator and single vinylaromatic monomer add from three still bottoms, through certain time of staying heel row
Go out.
According to the present invention, the kind of described noble gas can be the conventional selection of this area, such as,
Described noble gas can include but not limited at least one in nitrogen, argon and helium.
The kind of described atent solvent can be the conventional selection of this area, for example, it is possible to for having
The hydro carbons of 5-12 carbon atom and their cyclic analogs, preferably propane, butane, pentane,
Hexane, heptane, octane, decane, Pentamethylene., methyl cyclopentane, hexamethylene, cycloheptane, raffinate
At least one in oil, normal hexane and cyclooctane, more preferably raffinates oil, in normal hexane and hexamethylene
At least one.
According to the present invention, described single functionality organic lithium initiator can be normal in anionic polymerisation field
Single functionality organo-lithium compound for trigger monomer polymerization, it is preferable that described single functionality is organic
Lithium initiator can be for the compound as shown in formula (I):
RLi (I)
Wherein, R is the alkyl of straight or branched, cycloalkyl or aryl, preferably ethyl, propyl group,
Isopropyl, normal-butyl, sec-butyl, amyl group, hexyl, cyclohexyl, phenyl, aminomethyl phenyl or naphthalene
Base, more preferably normal-butyl or sec-butyl.
There is no particular limitation to the consumption of described single functionality organic lithium initiator for the present invention, Ke Yigen
Select according to the molecular size range needing the first polymerization reaction monomer obtained.Usually, needs are worked as
When obtaining bigger the first polymerization reaction monomer of molecular weight, then can reduce single functionality organolithium and cause
The consumption of agent；And when needing the first polymerization reaction monomer obtaining molecular weight, then can increase
The consumption of single functionality organic lithium initiator.As a rule, the conjugated diene list relative to 100g
Body, the consumption of described single functionality organic lithium initiator can be 2.22-2.86mmol.
According to the present invention, described polyfunctionality coupling agent can be selected from commonly used in the art multifunctional
Degree coupling agent, as long as making in olefin polymer containing star-like conjugated diolefin homopolymerization thing.Example
As, described polyfunctionality coupling agent can be polyfunctionality halogenide, preferably methyl trifluoro SiClx,
Methyl trichlorosilicane, methyl tribromo SiClx, methyl triiodo SiClx, methyl trifluoro stannum, methyl trichlorine
Change stannum, methyl tribromide stannum, methyl triiodide stannum, butyl trifluoro SiClx, butyl trichlorosilicane, fourth
Base tribromo SiClx, butyl triiodo SiClx, Silicon fluoride., Silicon chloride., Silicon bromide., tetraiodide
In silicon, tin tetrafluoride, butter of tin, tin tetrabromide, tin tetraiodide, butter of tin, butter of tin
At least one, more preferably Silicon chloride. and/or butter of tin, most preferably Silicon chloride..
According to the present invention, carry out coupling reaction to control only part the first polymeric reaction product, and remain
The first polymeric reaction product that remaining part is divided still is able to carry out follow-up termination reaction or the second polyreaction,
So that to olefin polymer in contain star-like conjugated diolefin homopolymerization thing, linear conjugated two simultaneously
Olefin homo and linear conjugated diene-monovinylarene copolymer, in described polyfunctionality coupling agent
The mol ratio of total coupling group and described single functionality organic lithium initiator can be 0.40-0.55:1,
It is preferably 0.45-0.54:1.In the present invention, the total coupling group in described polyfunctionality coupling agent is
Refer to the total content of coupling group in polyfunctionality coupling agent.
According to the present invention, the kind of described terminator can be selected from terminator commonly used in the art,
For example, it is possible to be water and/or alcohols, preferably at least in water, methanol, ethanol, isopropanol
Kind, more preferably water.Additionally, so that described coupling reaction product does not occurs the polymerization of coupling
A thing part carries out terminating reaction, and another part carries out the second polyreaction, described terminator and institute
The mol ratio stating single functionality organic lithium initiator can be 0.1-0.15:1, preferably 0.11-0.14:
1。
The consumption of described conjugated diene monomer and mono vinyl arenes monomer is not had the most especially by the present invention
Limit, such as, relative to the conjugated diene monomer of 100 weight portions, described mono vinyl arenes monomer
Consumption be 20-40 weight portion, more preferably 25-35 weight portion.Additionally, described conjugated diene list
The kind of body and mono vinyl arenes monomer has been described above being described, then this does not repeats.
According to the present invention, the method is additionally included in addition structure regulator and/or gel in step (1) and presses down
Preparation.The kind of described structure regulator can be the conventional selection of this area, for example, it is possible to be selected from
At least one in nitrogenous, oxygen-containing, sulfur-bearing, phosphorous polar compound, preferably ether, two fourths
Ether, dioxane, oxolane, glycol dimethyl ether, two dry diethylene glycol dimethyl ethers, diphenyl ether, three second
Amine, tetramethylethylenediamine, HMPA, potassium tert-butoxide, sodium alkyl benzene sulfonate and ethyl four
At least one in tetrahydrofurfuryl ether, more preferably oxolane and/or ethyl tetrahydrofurfuryl ether.Further
Ground, when using oxolane as structure regulator, the consumption of described oxolane can be polymerization
The 80-150ppm of system concentration；When using ethyl tetrahydrofurfuryl ether as structure regulator, described second
Base tetrahydrofurfuryl ether can be the 3-9ppm of polymerization system concentration.
The kind of described gel inhibitor can be the conventional selection of this area, for example, it is possible to selected from 1,2-
Butadiene, tertiary amoxy potassium (KTA)/Silicon chloride. (SiCl4), tetramethylethylenediamine (TMEDA)/1,2-fourth
At least one in diene and THF/1,2-butadiene.Additionally, the consumption of described gel inhibitor is permissible
For the 60-150ppm of polymerization system concentration, preferably 80-120ppm.
The condition of described first polyreaction is not particularly limited by the present invention, as long as enabling to institute
State conjugated diene monomer to carry out being polymerized and make the conversion ratio of monomer to reach >=97%, such as, institute
The condition stating the first polyreaction includes: polymerization temperature can be 40-130 DEG C, is preferably
70-110℃；Polymerization pressure can be 0.1-1.5MPa, preferably 0.2-0.5MPa；Polymerization time is permissible
For 20-70 minute, preferably 30-60 minute.
The condition of coupling reaction described in step (2) is also not particularly limited by the present invention, if energy
Enough make at least part of and described coupling agent generation coupling reaction in described first polymeric reaction product i.e.
Can, such as, the condition of described coupling reaction includes: coupling temperature can be 40-130 DEG C, is preferably
70-110℃；Coupling pressure can be 0.1-1.5MPa, preferably 0.2-0.5MPa；Coupling time is permissible
For 20-70 hour, preferably 30-60 hour.
The condition of described second polyreaction is also not particularly limited by the present invention, as long as enabling to
In the coupling reaction product that step (2) obtains, the part in non-coupling polymer is reacted with terminator,
And another part mono vinyl arenes monomer carries out polyreaction and makes mono vinyl arenes monomer convert
Rate reaches >=97%, and such as, the condition of described second polyreaction includes: polymerization temperature is permissible
For 40-130 DEG C, preferably 70-110 DEG C；Polymerization pressure can be 0.1-1.5MPa, is preferably
0.2-0.5MPa；Polymerization time can be 20-70 minute, preferably 30-60 minute.
In the present invention, described pressure refers both to gauge pressure.
Additionally, for the ageing-resistant performance improving described olefin polymer, generally complete the second polymerization
After reaction, in addition it is also necessary to described second polymeric reaction product is contacted with age resistor.Described age resistor can
Think the existing various material being prevented from ageing of rubber, for example, it is possible to be phenol antiager and/or
Amines antioxidants, specifically can be selected from 2,6 ditertiary butyl p cresol (being called for short Irganox 264), tertiary fourth
Base catechol, 2,2 '-methylene-bis-(4-methyl-6-tert-butylphenols) (be called for short Irganox 2246) and
One or more in 2,4-bis-(n-octylthiomethylene)-6-methylphenol (being called for short Irganox 1520).
On the basis of the total monomer weight added in whole polymerization process, the consumption of described age resistor is the most permissible
For 0.1-2 weight %.
After polyreaction completes, need the solvent removal in the olefin polymer that will finally give.
The method of desolvation is known to the skilled person, for example, it is possible to by alcoholization precipitation, be centrifuged
The modes such as separation, filtration, decant, steam cohesion by olefin polymer Precipitation from solvent,
Stripping mode can also be used to be separated off by the volatile solvent in olefin polymer.To this this area
Technical staff all can know, will not be described in great detail at this.
Present invention also offers the olefin polymer prepared by said method.
Additionally, present invention also offers described diene polymer as polystyrene resin and/or propylene
The application of the modifying agent of nitrile-butadiene styrene resin.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example:
1, in polymerization process, conjugated diene monomer, the conversion ratio of mono vinyl arenes monomer use
Shimadzu GC-14A flame gas chromatograph measures, and internal standard method calculates, and concrete calculating process is as follows:
St%=1-[(s/h)/(S/H)] × 100
Bd%=1-[(b/h)/(B/H)] × 100
Wherein, cinnamic peak area during s is the polymeric kettle outlet sample that GC measures；
B is the peak area of butadiene in the polymeric kettle outlet sample that GC measures；
H is the peak area of solvent in the polymeric kettle outlet sample that GC measures；
The unit inlet amount of styrene monomer, units/kg/h when S is polymerization；
The unit inlet amount of divinylic monomer, units/kg/h when B is polymerization；
H is the unit inlet amount of the solvent entering paradigmatic system, units/kg/.
2, the SV value of polymer refers to the styrene solution of described olefin polymer that concentration is 5 weight %
Viscosity at 25 DEG C, it uses Cannon-Fenske type viscometer to test.
3, polymer Mooney viscosity utilize Japan Shimudzu ML tester (preheat 1 minute,
Rotate 4 minutes at 100 DEG C, value) test.
4, the mensuration of gel content (Gel%): polymer samples is done in 50 DEG C in vacuum drying oven
Dry to constant weight, weigh, be designated as W1, then dissolve dried copolymer with styrene (cinnamic
Consumption makes the concentration of polymer be 5 weight %), fully dissolve 135 DEG C of vibrations, then use 300
Mesh stainless (steel) wire filtered polymeric solution, by polymer undissolved on stainless (steel) wire at vacuum drying oven
In in 100 DEG C be dried 4 hours, weigh, be designated as W2, calculate gel content value, gel content value meter
Calculation formula is as follows: gel content value (weight %)=(W2/W1) × 100 (weight %).
5, concentration is the mensuration of styrene solution colourity of described olefin polymer of 5 weight %: use
GB/T 9282.1-2008 standard, with platinum-cobalt titer as reference colour, measures by optical colorimetry.
6,1,2-structure (vinyl structure) in polymer monomer unit, cis-1,4-structure, trans
-Isosorbide-5-Nitrae-structural content uses Switzerland's Bruker AVANCE-400 type nuclear magnetic resonance chemical analyser test, room temperature
Measuring, liquid pool method, solvent is CS2.
7, polymer molecular weight and molecular weight distribution use Japan's Shimadzu LC-10A series gel infiltration color
Spectrometer GPC tests.
In following example and comparative example, star-like conjugated diolefin homopolymerization thing, linear conjugated alkadienes are equal
The content of polymers and linear conjugated diene-monovinylarene copolymer is calculated by inventory, tool
Body is as follows:
Content (weight %)=100 weight %-of linear conjugated diene-monovinylarene copolymer is star-like
The content of the content of conjugated diolefin homopolymerization thing-linear conjugated diene homopolymers；Wherein,
N1 is the total mole number of coupling group in polyfunctionality coupling agent used in polymerization process；
N2 is the total mole number of the terminator added in the 3rd still bottom in polymerization process；
N is the total mole number of single functionality organic lithium initiator used in polymerization process.
Embodiment 1
Olefin polymer that this embodiment provides for the present invention is described and preparation method thereof.
Reaction unit used by this embodiment includes three 5 liters of polymerization reaction kettles connected.At high pure nitrogen
Under protective atmosphere, control system head still residence time of material is 70 minutes, adds to first still bottom continuously
Raffinate oil 2490g/h, 1,3-butadiene 372g/h, oxolane 0.302g/h (100ppm), 1,2-fourth two
Alkene 0.343g/h and n-BuLi 0.595g/h, controls head still reaction temperature at 70 DEG C, and Stress control exists
0.3MPa, makes 1,3-butadiene carry out the first polyreaction in first still.First still reaction mass is confessed one's crime still
The overflow of still top is to the second still bottom (conversion ratio of first still exit 1,3-butadiene is 99.4%), with company
Continuous Silicon chloride. 0.178g/h (total coupling group of Silicon chloride. and the n-BuLi adding the second still bottom
Mol ratio be 0.45:1) contact after carry out coupling reaction, the second reaction kettle for reaction temperature is controlled
70 DEG C, Stress control is at 0.3MPa.Two still reaction masses by two still still top overflows to the 3rd still bottom,
(terminator water with the mol ratio of n-BuLi is with the water 0.022g/h being continuously added to the 3rd still bottom
The second polyreaction is carried out with styrene 159g/h, by the 3rd reaction kettle for reaction temperature after 0.13:1) contacting
Degree control 70 DEG C, Stress control is at 0.3MPa.At end still (three stills), outlet adds terminator isopropyl
Alcohol 0.234g/h terminates reaction (the three cinnamic conversion ratios in still exit are 99%), and adds monomer weight
The age resistor Irganox 1520 of amount 0.2%, then carries out devaporation desolventizing process, obtains glue
Olefin polymer J1, the molecular weight distribution of this olefin polymer J1 is Unimodal Distribution, and it makes a concrete analysis of survey
Test result is as shown in table 1.
Embodiment 2
Olefin polymer that this embodiment provides for the present invention is described and preparation method thereof.
Reaction unit used by this embodiment includes three 5 liters of polymerization reaction kettles connected.At high pure nitrogen
Under protective atmosphere, control system head still residence time of material is 40 minutes, adds to first still bottom continuously
Hexamethylene 5100g/h, 1,3-butadiene 567g/h, oxolane 0.465g/h, 1,2-butadiene 0.454g/h
With s-butyl lithium 0.806g/h, head still reaction temperature is controlled at 80 DEG C, Stress control at 0.4MPa,
Making 1,3-butadiene carry out described first polyreaction in first still, overflows in first still reaction mass still still top of confessing one's crime
It flow to the second still bottom (conversion ratio of first still exit 1,3-butadiene is 99%), and be continuously added to the
Silicon chloride. 0.268g/h (total coupling group of Silicon chloride. and the mol ratio of s-butyl lithium of two still bottoms
For 0.50:1) carry out coupling reaction after contact, temperature is controlled 80 DEG C, Stress control is at 0.4MPa.
Two still reaction masses by two still still top overflows to the 3rd still bottom, with the water being continuously added to the 3rd still bottom
0.034g/h (terminator water is 0.15:1 with the mol ratio of n-BuLi) and styrene 142.3g/h contacts
After carry out the second polyreaction, the 3rd reaction kettle for reaction temperature is controlled 80 DEG C, Stress control exists
0.4MPa.(three stills go out to add terminator isopropanol 0.340g/h termination reaction in end still (three stills) outlet
At Kou, cinnamic conversion ratio is 98%), and add the age resistor Irganox of monomer weight 0.2%
1520, then glue is carried out devaporation desolventizing process, obtains olefin polymer J2, this alkene
The molecular weight distribution of polymer J2 is Unimodal Distribution, and its concrete analysis test result is as shown in table 1.
Embodiment 3
Olefin polymer that this embodiment provides for the present invention is described and preparation method thereof.
Reaction unit used by this embodiment includes three 5 liters of polymerization reaction kettles connected.At high pure nitrogen
Under protective atmosphere, control system head still residence time of material is 30 minutes, adds to first still bottom continuously
Mixed solvent (hexamethylene and normal hexane, weight ratio is 88:12) 6600g/h, 1,3-butadiene
986g/h, ethyl tetrahydrofurfuryl ether 0.049g/h (6ppm), 1,2-butadiene 0.910g/h and n-BuLi
1.803g/h, controls head still reaction temperature at 90 DEG C, and Stress control, at 0.5MPa, makes 1,3-butadiene
In first still, carry out described first polyreaction, then reaction mass from first still still top overflow to the second still
Bottom (conversion ratio of first still exit 1,3-butadiene is 99%), and is continuously added to the second still bottom
Silicon chloride. 0.658g/h (total coupling group of Silicon chloride. and the mol ratio of n-BuLi are 0.55:1)
Carry out coupling reaction after contact, the second reaction kettle for reaction temperature is controlled 90 DEG C, Stress control exists
0.5MPa.Two still reaction masses to the 3rd still bottom, and are continuously added to the 3rd still by two still still top overflows
The water 0.169g/h (terminator isopropanol is 0.10:1 with the mol ratio of n-BuLi) of bottom and styrene
657.4g/h contact after carry out the second polyreaction, the 3rd reaction kettle for reaction temperature is controlled 90 DEG C,
Stress control is at 0.5MPa.Add terminator isopropanol 0.592g/h in end still (three stills) outlet to terminate
Reaction (the three cinnamic conversion ratios in still exit are 99%), and add the anti-old of monomer weight 0.2%
Agent Irganox 1520, then carries out devaporation desolventizing process, obtains olefin polymer glue
J3, the molecular weight distribution of this olefin polymer J3 is Unimodal Distribution, and it makes a concrete analysis of test result such as table 1
Shown in.
Comparative example 1
This comparative example is for olefin polymer that reference is described and preparation method thereof.
The olefin polymer of reference is prepared according to the method for embodiment 1, except that, in course of reaction
Being added without Silicon chloride., obtain reference olefin polymer DJ1, it is as shown in table 1 that it analyzes test result.
Comparative example 2
This comparative example is for olefin polymer that reference is described and preparation method thereof.
The olefin polymer of reference is prepared according to the method for embodiment 1, except that, in course of reaction
Being added without the styrene containing water, obtain reference olefin polymer DJ2, it analyzes test result such as table 1
Shown in.
Table 1
Test case
Test case is used for illustrating that olefin polymer is as polystyrene resin and/or acrylonitrile-butadiene-benzene
The application of the modifying agent of vinyl.
In 2 liters of stainless steel cauldrons with stirring, mass suspension method is used to prepare shock resistance polyphenyl second
Olefine resin.
It is firstly added 1232 grams of styrene, then is separately added into olefin polymer J1-J3 and the reference of 70g
Olefin polymer DJ1-DJ2, is subsequently added into 70 grams of ethylbenzene, carries out radical initiator after 28 grams of white oils
The bulk-suspension polymerization caused.Initiation reaction temperature is 110 DEG C, and initiator uses 1,1-diperoxy uncle
Butyl cyclohexane (DP-275B), initiator amount is 450ppm, and speed of agitator is 350 revs/min.
Respectively obtain MPS PS1-PS3 and DPS1-DPS2, in accordance with the following methods to its shock resistance
Intensity and glossiness are tested:
(1) impact strength: use U.S. CE AST company RESIL IMPACTOR instrument, ASTM
D256 standard testing, wherein, test temperature is 25 DEG C.Test result is as shown in table 2.
(2) surface gloss (45 °): use Switzerland's ZLR1050 vancometer, ASTM D1003
Standard testing, wherein, the numerical value of glossiness is the highest more good.Acquired results is as shown in table 2.
Table 2
By the data of above-described embodiment and comparative example it can be seen that use the alkene that the inventive method obtains
Polymer has suitable Mooney viscosity (the Mooney viscosity ML at 100 DEG C1+4For 45-70), it is easy to after
Continuous processing, and there is suitable SV value (0.02-0.04Pa s), use the olefinic polymerization of the present invention
Resin is modified by thing, on the premise of the mechanical property ensureing resin, can be effectively improved resin
Glossiness.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the technology concept of the present invention, can be to the skill of the present invention
Art scheme carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as
It is without prejudice to the thought of the present invention, and it should be considered as content disclosed in this invention equally.
Claims (12)
1. an olefin polymer, it is characterised in that described olefin polymer contains star-like conjugated diene
Hydrocarbon homopolymer, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene copolymer,
The molecular weight distribution of described olefin polymer is Unimodal Distribution, described olefin polymer door at 100 DEG C
Buddhist nun's viscosity ML1+4For 45-70, and the styrene solution of the described olefin polymer that concentration is 5 weight %
Viscosity at 25 DEG C is 0.02-0.04Pa s.
Olefin polymer the most according to claim 1, wherein, total with described olefin polymer
On the basis of weight, the content of described star-like conjugated diolefin homopolymerization thing is 40-55 weight %, described line style
The content of conjugated diolefin homopolymerization thing is 10-15 weight %, described linear conjugated diene-monovinylarene
The content of copolymer is 35-45 weight %.
Olefin polymer the most according to claim 1 and 2, wherein, with described olefin polymer
Gross weight on the basis of, monovinylarene in described linear conjugated diene-monovinylarene copolymer
The content of homopolymerization section is 20-40 weight %, and described monovinylarene homopolymerization section refers to described linear conjugated
Continuously containing six and more than six monovinylarenes on diene-monovinylarene copolymer strand
The content of construction unit；
Preferably, on the basis of the gross weight of described olefin polymer, described linear conjugated diene-mono-second
In alkenyl arene copolymer, the content of the micro-block of monovinylarene is 0-3 weight %, described mono-vinyl
The micro-block of aromatic hydrocarbons refers to contain continuously on described linear conjugated diene-monovinylarene copolymer strand
The content of five and less than five monovinylarene construction units.
Olefin polymer the most according to claim 1 and 2, wherein, with described olefin polymer
On the basis of the content of middle conjugated diene construction unit, in described conjugated diene construction unit 1,2-structure list
The content of unit is 5-15 weight %；
Preferably, in described olefin polymer on the basis of the content of conjugated diene construction unit, institute
The content stating cis in conjugated diene construction unit-Isosorbide-5-Nitrae-construction unit is 25-40 weight %, anti-form-1,4-
The content of construction unit is 45-65 weight %.
Olefin polymer the most according to claim 1, wherein, the number of described olefin polymer is equal
Molecular weight is 50,000-70,000, and molecular weight distributing index is 1.5-1.8.
6. a preparation method for olefin polymer, wherein, the method includes:
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer
And atent solvent is continually introduced into the continuous polymerization reaction unit including at least three series polymerizations reactor
First still in carry out the first polyreaction；
(2) conversion ratio >=97% of conjugated diene monomer described in described first still exit is controlled, and will
Polyfunctionality coupling agent is continually introduced in second polymerization reaction kettle of described continuous polymerization reaction unit
Row coupling reaction；Total coupling group in the described polyfunctionality coupling agent added in unit interval and list
The mol ratio of the described single functionality organic lithium initiator added in bit time is 0.40-0.55:1；
(3) terminator and mono vinyl arenes monomer are continually introduced into described continuous polymerization reaction unit
3rd polymerization reaction kettle contacts with the product from described second polymerization reaction kettle carry out
Dimerization is reacted, and controls mono vinyl arenes monomer described in described 3rd polymerization reaction kettle exit
Conversion ratio is >=97%；In unit interval, the addition interior with the unit interval of the described terminator of addition is described
The mol ratio of single functionality organic lithium initiator is 0.1-0.15:1.
Method the most according to claim 6, wherein, described polyfunctionality coupling agent is multifunctional
Degree halogenide, preferably methyl trifluoro SiClx, methyl trichlorosilicane, methyl tribromo SiClx, methyl three
Iodate silicon, methyl trifluoro stannum, tin methyltrichloride, methyl tribromide stannum, methyl triiodide stannum,
Butyl trifluoro SiClx, butyl trichlorosilicane, butyl tribromo SiClx, butyl triiodo SiClx, tetrafluoride
Silicon, Silicon chloride., Silicon bromide., silicon tetraiodide, tin tetrafluoride, butter of tin, tin tetrabromide,
At least one in tin tetraiodide, butter of tin, butter of tin, more preferably Silicon chloride. and/or four
Stannic chloride, most preferably Silicon chloride..
Method the most according to claim 6, wherein, relative to the conjugated diene of 100 weight portions
Hydrocarbon monomer, the consumption of described mono vinyl arenes monomer is 20-40 weight portion, preferably 25-35 weight
Part.
9. according to the method described in claim 6 or 7, wherein, the method is additionally included in step (1)
Middle addition structure regulator and/or gel inhibitor；
Preferably, described structure regulator is in nitrogenous, oxygen-containing, sulfur-bearing, phosphorous polar compound
At least one, preferably ether, butyl oxide, dioxane, oxolane, glycol dinitrate
Ether, two dry diethylene glycol dimethyl ethers, diphenyl ether, triethylamine, tetramethylethylenediamine, HMPA,
At least one in potassium tert-butoxide, sodium alkyl benzene sulfonate and ethyl tetrahydrofurfuryl ether, more preferably tetrahydrochysene
Furan and/or ethyl tetrahydrofurfuryl ether；
Preferably, described gel inhibitor is selected from 1，2-butadiene, tertiary amoxy potassium/Silicon chloride., tetramethyl
At least one in base ethylenediamine/1,2-butadiene and THF/1,2-butadiene.
10. according to the method described in claim 6 or 7, wherein, the condition of described first polyreaction
Including: temperature is 40-130 DEG C, and pressure is 0.1-1.5MPa, and the time is 20-70 minute；
Preferably, the condition of described coupling reaction includes: temperature is 40-130 DEG C, and pressure is
0.1-1.5MPa, the time is 20-70 minute；
Preferably, the condition of described second polyreaction includes: temperature is 40-130 DEG C, and pressure is
0.1-1.5MPa, the time is 20-70 minute.
11. olefin polymers prepared by the method described in any one in claim 6-10.
In 12. claim 1-5 and 11, the olefin polymer described in any one is as polystyrene tree
The application of the modifying agent of fat and/or acrylonitrile-butadiene-styrene resin.
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